JP2012509389A - Synthetic inorganic flame retardants, methods for their preparation and their use as flame retardants - Google Patents

Abstract

Quite unexpectedly, the general formula M ^II ₃ M ^III ₂ (OH) ₁₂ (where M ^II represents a divalent metal ion of group IIA of the periodic table, in particular an alkaline earth metal ion, and M ^III represents Conventionally such as ATH and MDH by optimally modifying the crystal structure of hydrogarnets of group IIIA trivalent metal ions, particularly aluminum) with suitable amounts of combined silicates and / or phosphates It is possible to produce a flame retardant having a higher flame retardant efficiency than that of inorganic flame retardants and a thermal stability higher than that of ATH. (Here ^{M II} and ^{M III} is as defined above) general formula _{^{M II 3 M III 2 (OH}} ) 12 having a cubic crystal form and can generate a synthetic hydrogarnet, these synthetic hydrogarnet also highly flame retardant efficiency It was also found to show.
[Selection] Figure 1

Description

  The present invention relates to synthetic inorganic flame retardants, methods for their preparation and their use as flame retardants.

  Conventionally, the efficiency of inorganic flame retardants often used in polymers such as aluminum trihydroxide (ATH) and magnesium hydroxide (MDH) is limited. High filling is required to pass the relevant burn test. In some cases, even when used at maximum fill, certain flammability tests are demanding, or the mechanical, rheological, or electrical properties of the final product are destroyed. Furthermore, aluminum trihydroxide begins to decompose at about 200 ° C., limiting its application to polymers that are processed at similar or lower temperatures.

  Provided is a novel inorganic flame retardant having a high flame retardant efficiency that can lower the filler loading than conventional products such as aluminum trihydroxide and magnesium hydroxide, preferably aluminum trihydrate It would be highly beneficial to find a way to obtain new flame retardants that can be used effectively in polymeric materials that have a sufficiently higher thermal stability than oxides and require processing temperatures above 200 ° C.

  The present invention has been made to satisfy the aforementioned advantages with economically attractive main components.

According to the present invention, surprisingly, the general formula M ^II ₃ M ^III ₂ (OH) _12, where M ^II represents a divalent metal ion of group IIA of the periodic table, in particular an alkaline earth metal ion, and M ^III is The addition of alkali hydroxide to the synthesis of hydrogarnets of group IIIA trivalent metal ions of the periodic table IIIA, especially aluminum) can transform the crystal shape from an irregular, nearly spherical crystal to a clearly defined cube. It's been found. These synthetic hydrogarnet compounds have higher flame retardant efficiency and higher thermal performance than aluminum trihydroxide (ATH) than conventional inorganic flame retardants such as aluminum trihydroxide (ATH) and magnesium hydroxide (MDH) It can be used as a flame retardant material having stability.

Furthermore, quite unexpectedly, the crystal structure of the hydrogarnet of the general formula M ^II ₃ M ^III ₂ (OH) ₁₂ (M ^II and M ^III are as defined above) is converted to a suitable amount of combined silicate and / or phosphoric acid. By appropriately modifying with salt, it is synthesized in the presence of alkali hydroxide with higher flame retardant efficiency than conventional inorganic flame retardants such as aluminum trihydroxide (ATH) and magnesium hydroxide (MDH) It has been discovered that flame retardant materials are produced that have higher thermal stability than hydrogarnet. A flame retardant compound of the empirical formula M ^II ₃ M ^III ₂ (OH) _12-4x (SiO ₄ ) _x when only silicate is incorporated by adding silicate or phosphate ions to the crystal structure; Experimental Formula M Incorporating Phosphate Only Experimental Formula M ^II ₃ M ^III ₂ Oy (OH) _12-5y (PO ₄ ) _y Flame Retardant Compound, Or Incorporating Silicate And Phosphate _{^{II 3 M III 2 O y (}} OH) 12-5y-4x (PO 4) y (SiO 4) a flame retardant compound of _x are obtained, respectively.

The crystal structure of the silicon-modified and / or phosphorus-modified composition relates to hydrogarnet (ie M ^II ₃ M ^III ₂ (OH) ₁₂ ) and garnet (ie M ^II ₃ M ^III ₂ (SiO ₄ ) ₃ ). Flame retardants differ in composition and properties from garnet and hydrogarnet. Silicon-modified and / or phosphorus-modified compositions generally have an octahedral crystal shape.

  The crystal shape of the hydrogarnet compound of the present invention which is not silicon-modified and / or phosphorus-modified is generally cubic. The hydrogarnet crystals produced by US Pat. No. 3,912,671 were reported to be spherical in shape and produced irregular isometric polyhedra when following the procedures disclosed therein.

  The structural and compositional changes resulting from the present invention provide unexpected benefits in the properties of the flame retardant. For example, as shown in Tables 1 to 3 below, it was found that the composition of the present invention has a greater thermal stability than ordinary hydrogarnet.

Thus, the present invention provides, inter alia, a flame retardant comprising a synthetic hydrogarnet that is optionally modified and modified by including silicates and / or phosphates in its crystal structure. The flame retardant provided by the present invention is further described in that the crystal structure of the flame retardant is related to hydrogarnet, that is, M ^II ₃ M ^III ₂ (OH) ₁₂ . This type of synthetic flame retardant is characterized by providing high heat dissipation properties when incorporated at a suitable concentration suitable for an ethylene vinyl acetate specimen that undergoes combustion in a conical calorimeter. For example, if the second heat dissipation peak can be reached, the time to reach the second heat dissipation peak is long and the second maximum heat dissipation (if any) is low. The absence of the second peak or its lower maximum is a consequence of char formation and prevents flammable gases from entering the gas phase and igniting.

In a preferred embodiment, the present invention provides a synthetic inorganic modified hydrogarnet flame retardant having the following empirical formula (i) and the following characteristics (ii):
(I) has the empirical formula ^{_{M II 3 M III 2 O y}} (OH) 12-5y-4x (PO 4) y (SiO 4) x,
Where M ^II is one or a mixture of more than one alkaline earth metal (preferably Ca), x and y are preferably numbers in the range of 0 to about 1.5, and x + y Is a number in the range of 0 to about 1.5, preferably about 0.05 to about 1.5, more preferred range is about 0.1 to about 1.5, and even more preferred range. Is from about 0.05 to about 1.2; (ii) has the following properties:
a) the median number of particle diameters, d ₅₀ , is a number in the range of about 0.5 μm to about 10 μm as determined by laser diffraction;
b) a surface area in BET determination is in the range of about 0.5 m ² / g to about ^{30 m} 2 / g, preferably about ^{1 m} 2 / g to about ^{30 m} 2 / g, more preferably from about 0.5 m ² / g to about ^{15 m} 2 / g, about ^{1 m} 2 / g to about ^{15 m} 2 / g, even more preferably about ^{1 m} 2 / g to about ^{10 m} 2 / g, about ^2m 2 / g to about ^{10 m} 2 / g, as well as,
c) The calorimetric temperature of the heating rate of 1 ° C. per minute and 105 ° C. and 2% moisture loss after 4 hours pre-drying is less than 230 ° C., preferably less than 240 ° C., more preferably less than 250 ° C.

  More preferably, the synthetic inorganic flame retardant has a surface water content determined by an infrared moisture balance at 105 ° C. of less than 0.7% by weight, preferably less than 0.5% by weight, and contains sodium oxide determined by flame colorimetry. It is further characterized in that the amount is less than 0.5% by weight.

Also provided by the present invention is a process technique for producing the synthetic flame retardant described above. For example, the present invention provides a process for preparing a synthetic inorganic hydrogarnet that is optionally modified with a suitable amount of silicate and / or phosphate, the process comprising:
● Stirring the mixture formed from (1) Group IIIA metal source (especially aluminum source),
(2) Group IIA metal source (especially alkaline earth metal source),
(3) optionally a silicon source (especially an aqueous silicate aqueous solution, eg (i) one or more of aqueous solutions of eg NaSiO ₃ or Na ₂ Si ₃ O ₇ available as “water glass”, and / or (ii) ) Powdered amorphous or crystalline silicon dioxide) and / or (4) optionally a phosphorus source (especially an aqueous phosphate solution such as phosphoric acid, Na ₃ PO ₄ , Na ₂ HPO ₄ , NaH ₂ PO). ₄ , alkali or ammonium phosphates such as ₄ , alkali or ammonium diphosphates such as Na ₄ P ₂ O ₇ and / or alkali or ammonium polyphosphates),
Wherein (1), (2), (3) and / or (4) are independent and / or their respective hydrates are in a solid state or in an aqueous solution;
(5) alkali metal hydroxide,
And heating the stirred mixture at a temperature in the range of about 50 ° C to about 100 ° C.
Optionally cooling the reaction product or cooling the reaction product and recovering the reaction product,
In the step, the ratio of the Group IIIA metal source to the Group IIA metal source used in forming the mixture is within a range of about 1: 1 to about 2: 1 in terms of a molar ratio of Group IIA metal to Group IIIA metal. In practice, the silicon source used to form the mixture is silicic acid in an amount ranging from about 0.05 mole to about 1.5 mole per mole of synthetic inorganic hydrogarnet to be formulated. The phosphorus source that provides the salt and / or, when present, used to form the mixture, is an amount of phosphorus ranging from about 0.05 mole to about 1.5 moles per mole of the synthetic inorganic hydrogarnet to be formulated. Provide the acid salt. A preferred ratio of the silicon source used for forming the mixture and / or the phosphorus source used for forming the mixture ranges from about 0.1 mol to about 1.5 mol of silicate and / or phosphate. And more preferably providing an amount of silicate and / or phosphate in the range of about 0.05 mole to about 1.2 mole per mole of synthetic inorganic hydrogarnet to be formulated. . In general, each silicon atom from a silicon source forms one silicate ion in the modified synthetic inorganic hydrogarnet, and each phosphorus atom from the phosphorus source forms one phosphate ion in the modified synthetic inorganic hydrogarnet. Form.

Many of the reactants that can be used in the process are poorly soluble in water, and only a small fraction of one or more reactants is in solution under the reaction conditions used in the process, and the reaction is dissolved. It should be noted that this occurs via ions. Thus, at any given time instant, only a small amount of the reactant may dissolve in the water, and in order to prepare the ions necessary for the reaction to continue so that this type of ion is consumed in the reaction. A previously undissolved amount of reactant is placed in the aqueous solution. Thus, the reaction can proceed smoothly even with compounds not generally described as water soluble, such as aluminum trihydroxide (ATH) or Al ₂ O ₃ .

The preferred process of the present invention relates to the production of synthetic flame retardants, which are modified by employing a suitable amount of silicate and / or phosphate in the process. This process includes:
Stirring a mixture formed from an aluminum source, calcium source, water, silicon and / or phosphorus source, and alkali metal hydroxide, and heating the stirred mixture at a temperature in the range of about 50 ° C to 100 ° C. The aluminum source is (i) aluminum hydroxide, boehmite, pseudoboehmite, aluminum oxide or a mixture of any two or more of the foregoing, and (ii) in powder form, the calcium source is (i) inorganic salt, water An oxide, or an oxide of calcium, including hydrates, and (ii) in powder form,
Optionally cooling the reaction product or cooling the reaction product,
as well as,
● Recover reaction products,
The step of forming the mixture is characterized in that the ratio of the aluminum source to the calcium source used in forming the mixture is within a range of about 1: 1 to about 2: 1 in terms of a CA: Al molar ratio. The silicon source used in the process provides an amount of silicate ranging from about 0.05 mole to about 1.5 mole, preferably about 0.1 mole of silicate per mole of synthetic flame retardant produced. ~ About 1.5
In the molar range, more preferably in the range of about 0.05 mol to about 1.2 mol, and / or the phosphorus source used to form the mixture ranges from about 0.05 mol to about 1.5 mol. The amount of phosphate provided and preferably in the range of about 0.1 mol to about 1.5 mol, more preferably about 0.05 mol to about 1.5 mol of phosphate per mol of synthetic flame retardant produced. The range is about 1.2 moles.

  These and other features, embodiments and advantages of the present invention will become more apparent from the following description, the accompanying drawings and the appended claims.

It is a cone-type calorimeter heat radiation rate curve of Example 6 (invention) and Example 9 (comparison) of this invention. It is a cone-type calorimeter heat radiation rate curve of Example 7 (invention) and Example 9 (comparison) of this invention. It is a cone-type calorimeter heat radiation rate curve of Example 8 (invention) and Example 9 (comparison) of this invention. It is a cone-type calorimeter heat radiation rate curve of Example 10 (invention) and Example 12 (comparison) of this invention. It is a cone-type calorimeter heat radiation rate curve of Example 11 (invention) and Example 12 (comparison) of this invention. It is a SEM micrograph of the modified hydro garnet formed in Example 1 of the present invention. It is a SEM micrograph of the hydro garnet formed in Example 5 of this invention. It is a SEM micrograph of the hydro garnet formed based on US Patent 3,912,671.

  Without wishing to be bound by theory, the structure of the compounds of the invention in which silicate and / or phosphate ions are present is the structure of the four hydroxide ions exchanged for silicate or phosphate ions. With some arrangements, it is considered to have the same atomic arrangement as the hydrogarnet, and in the crystal structure the four oxygen atoms of the silicate or phosphate are in the same place as the oxygen atoms of the four hydroxide ions It seems to be.

As described above, the novel flame retardant of the present invention is represented by the following general formula (1):
Where M ^II is a Group IIA metal atom, typically Ca, Sr, Ba, or a mixture of at least two of these, or one or more of these and a minor proportion of Mg (ie about 50% by weight). M ^III is a Group IIIA metal atom, particularly aluminum, but may be a mixture with a small amount of B, Ga, In or Tl (eg, less than about 20% by weight), or these 2 A mixture of two or more, x and y are preferably numbers ranging from 0 to about 1.5, and x + y is a number ranging from 0 to about 1.5, preferably from about 0.05 to about 1.5. A number of 1.5, a more preferred range is from about 0.1 to about 1.5, and a further preferred range is from about 0.05 to about 1.2. There may be a flame retardant and trace amounts of other metal atoms that do not adversely affect the thermal stability of the flame retardant. If no silicon or phosphorus source is used in the synthesis of the product, the product is represented by the general formula M ^II ₃ M ^III ₂ (OH) ₁₂ , where M ^II and M ^III are as described in the general formula (1) above. It is synonymous. If no phosphorus source is used in the synthesis of the product, the product is represented by the following general empirical formula:
Wherein M ^II and M ^III are as defined in the general formula (1) above, and x is a number in the range of 0 to about 1.5, preferably in the range of about 0.05 to about 1.5. A number, more preferably a number in the range of about 0.05 to about 1.2. If no silicon source is used in the synthesis of the product, the product is represented by the following general empirical formula:
Wherein M ^II and M ^III are as defined in the general formula (1) above, and y is a number in the range of 0 to about 1.5, preferably in the range of about 0.05 to about 1.5. A number, more preferably a number in the range of about 0.05 to about 1.2.

A preferred flame retardant of the present invention is represented by the following general empirical formula (2):
Where M ^II is a Group IIA metal atom, typically Ca, Sr, Ba, or a mixture of at least two of these, or a minor ratio of one or more thereof to Mg (ie, less than about 50% by weight). X and y are preferably numbers in the range of 0 to about 1.5, and x + y is a number in the range of 0 to about 1.5, preferably about 0.05 to about 1.5. A number in the range of 1.5, more preferably a number in the range of about 0.1 to about 1.5, and even more preferably a number in the range of about 0.05 to about 1.2. Further, here, there may be trace amounts of flame retardants and other metal atoms that do not adversely affect the thermal stability of the flame retardant. If no silicon or phosphorus source is used in the synthesis of the product, the product is represented by the general formula M ^II ₃ M ^III ₂ (OH) ₁₂ , where M ^II is as defined in the general formula (2) above. . If no phosphorus source is used in the synthesis of the product, the product is represented by the following general empirical formula:
In the formula, M ^II is as defined in the general formula (2), and x is a number in the range of 0 to about 1.5, preferably a number in the range of about 0.05 to about 1.5. More preferably, the number is in the range of about 0.05 to about 1.2. If no silicon source is used in the synthesis of the product, the product is represented by the following general empirical formula:
Wherein M ^II is as defined in the general formula (2) above, and y is a number in the range of 0 to about 1.5, preferably a number in the range of about 0.05 to about 1.5. More preferably, the number is in the range of about 0.05 to about 1.2.

Particularly preferred flame retardants of the present invention are represented by the following general empirical formula (3):
Where x and y are numbers in the range of 0 to about 1.5, and x + y is a number in the range of about 0 to about 1.5, preferably about 0.05 to about 1.5. The number of ranges, more preferred ranges are from about 0.1 to about 1.5, and even more preferred ranges are from about 0.05 to about 1.2. As above, there can be flame retardants and trace amounts of other metal atoms that do not adversely affect the thermal stability of the flame retardant. If no silicon source or phosphorus source is used in the synthesis of the product, the product is represented by the general formula Ca ₃ Al ₂ (OH) ₁₂ . If no phosphorus source is used in the synthesis of the product, the product is represented by the following general empirical formula:
Where x is a number in the range of 0.05 to about 1.5, preferably a number in the range of about 0.1 to about 1.5, more preferably about 0.05 to about 1.2. The number of ranges. If no silicon source is used in the synthesis of the product, the product is represented by the following general empirical formula:
Where y is a number in the range of 0.05 to about 1.5, preferably a number in the range of about 0.05 to about 1.5, more preferably about 0.05 to about 1.2. The number of ranges.

The flame retardant of the present invention (the flame retardant of the above general formula (1), (1A), (1B), (2), (2A), (2B), (3), (3A) or (3B)) is effective. A flame retardant with increased properties, further characterized by enhanced thermal stability. In addition, it is believed that by including silicate and / or phosphate in the crystal structure, the crystal growth characteristics of the flame retardant of the present invention are positively influenced as a result. In turn, there can be beneficial effects on various properties of flame retardants, including purity. In this connection, the particularly preferred flame retardant of the present invention (the above general formula (1), (1A), (1B), (2), (2A), (2B), (3), (3A) or (3B) In which at least about 98% by weight of M ^II is Ca and at least about 98% by weight of M ^III is Al.

  The flame retardant of the present invention is useful for a wide variety of flame retardant applications. For example, the flame retardant can be effectively used in a wide variety of polymers such as thermoplastic and thermosetting polymers, resins, and elastic bodies (eg, natural and synthetic rubbers). The preferred use of the flame retardant of the present invention is as a polyethylene and its copolymer component or polypropylene and its copolymer component for electric wires and cable wires, and as a resin component such as an epoxy resin for printed circuit boards. is there. In these applications, the improved thermal stability provided by merging the flame retardant with a silicate and / or phosphate moiety is quite important and numerically comparable but comparable The high thermal stability compared to the material appears to be relatively small in degrees Celsius (° C). Thus, when forming flame retardant electric wires and cable wires, for example, higher processing temperatures and higher throughput can be obtained during extrusion molding. Can be quite important to the person.

As described above, various raw materials can be used in formulating the flame retardant of the present invention. Non-limiting examples of Group IIA compounds include magnesium bromide, magnesium chloride, magnesium iodide, magnesium hydroxide, magnesium oxide, magnesium nitrate, magnesium phosphate, magnesium sulfate, calcium bromide, calcium chloride, calcium iodide, water Calcium oxide, calcium oxide, calcium nitrate, calcium phosphate, calcium sulfate, strontium bromide, strontium chloride, strontium iodide, strontium hydroxide, strontium oxide, strontium nitrate, strontium phosphate, strontium sulfate, barium bromide, barium chloride, iodine Barium fluoride, barium hydroxide, barium oxide, barium nitrate, barium phosphate, barium sulfate, or a mixture of two or more of the foregoing. Thus, the Group IIA raw materials used are one or more inorganic salts of Group IIA metals or mixtures of Group IIA metals, or mixtures of one or more inorganic Group IIA metal salts with other trace amounts of Group IIA metal salts. For example calcium hydroxide or magnesium oxide or calcium oxide with magnesium oxide. Among these, calcium compounds lacking halogen are preferable, and calcium hydroxide and calcium oxide are more preferable. In a preferred embodiment of the invention, the median number d ₅₀ of the starting material particle size is less than ₅₀ μm, preferably less than 10 μm, more preferably less than 2 μm.

Similarly, a wide variety of Group IIIA compounds can be used as raw materials for formulating the flame retardant of the present invention. Non-limiting examples of Group IIIA compounds include aluminum hydroxide, boehmite, pseudoboehmite, aluminum oxide, aluminum bromide hexahydrate, aluminum chloride hexahydrate, aluminum iodide hexahydrate, aluminum nitrate and its water Japanese hydrate, aluminum sulfate and its hydrate, aluminum phosphate, gallium nitrate, gallium oxide, gallium oxychloride, gallium sulfate, gallium trichloride, gallium tribromide, indium trichloride, indium nitrate, indium sulfate, or the aforementioned A mixture of two or more of the following: Of these, calcium compounds lacking halogen are preferred. In a preferred embodiment of the present invention, the median number d ₅₀ of the starting material particle size is less than ₅₀ μm, preferably less than 30 μm, more preferably less than 20 μm.

  In some embodiments of the invention, the starting material is ground by any suitable dry or wet grinding process known in the art to obtain the desired particle size distribution. The grinding step is for i) Group IIA source only, ii) Group IIIA source only, iii) Both Group IIA and IIIA sources, or iv) Synthesis of products of the invention with Group IIA and Group IIIA sources. It can be applied to a mixture having a molar ratio required for the above.

  It has been observed that the particle size of the product is affected by the particle size of the Group IIA metal salt. In general, the larger the particle size of the Group IIA metal salt, the larger the product particle size. Also, if a group exists in the Group IIA metal salt, the product often forms a group. Grinding of the Group IIA metal salt is a preferred strategy to minimize or eliminate aggregation.

The silicon source used in the formulation of the flame retardant of the present invention can vary. A particularly useful silicon source is an aqueous silicate solution, for example (i) one or more solutions of eg NaSiO ₃ or Na ₂ Si ₃ O ₇ and / or (ii) powdered form as “water glass”. Non-crystalline or crystalline silicon dioxide. The phosphorus source can be an aqueous phosphate solution, for example phosphoric acid, an alkali such as Na ₃ PO ₄ , Na ₂ HPO ₄ , NaH ₂ PO ₄ or an ammonium phosphate, an alkali such as Na ₄ P ₂ O ₇ or ammonium. It can be a diphosphate, and / or an alkali or ammonium polyphosphate, all of these phosphorus compounds and their respective hydrates in solid or aqueous solution.

  First, at least some of the water that forms the aqueous phase is charged to the reactor, and charged to the appropriate ratio of Group II metal salt and Group III metal salt (individually or as a preformed mixture) and used. In some cases, it is desirable to subsequently fill the silicon source and / or the phosphorus source. If necessary, the silicon source and / or the phosphorus source may be added before the group II metal source and / or the group III metal source.

  The mixture formed from the Group IIIA metal source, the Group IIA metal source, the optional source of silicon and / or phosphorus, and the alkali metal hydroxide should be a substantially homogeneous mixture. Accordingly, the mixture is generally agitated and mixed to form a substantially homogeneously prepared mixture. The mixture is typically heated and stirred at one or more elevated temperatures, for example, at a temperature in the range of about 50 ° C to about 100 ° C. Agitation and mixing of the components is performed under these temperature conditions for at least a period sufficient to form the flame retardant product of the present invention. Usually, the length of the warming period is not critical since it can vary depending on the use temperature and the degree of homogeneity of the stirred mixture. Typically, the mixture is agitated or stirred at the elevated temperature for at least about 10 minutes, and optionally at least about 30 minutes for the entire period.

  Any suitable reaction temperature or reaction temperature sequence that produces acceptable reaction rates can be utilized. Typically, the reaction is carried out at a temperature in the range of about 50 ° C to about 100 ° C. It should be noted that this reaction is not a precipitation reaction, but instead is a recrystallization through a partial aqueous solution in which all calcium and aluminum are never completely dissolved.

  The suspension obtained with the flame retardant according to the invention is then filtered to remove impurities and washed to form a filter cake. The filter cake is then dried by any of the known techniques for drying filter cakes. In some exemplary embodiments, the filter cake is dried using a spin flash dryer, other continuously operated flash dryers, or cell disruption techniques in the production of inorganic fillers. In all techniques, according to the consistency of the filter cake, the filter cake is transferred to the dryer with suitable feeding equipment, such as a screw conveyor, and dispersed with one or more rotors. Hot gas, typically air, is directed to a dryer prepared for fast evaporation of the water contained in the filter cake. The hot gas stream carries fine deagglomerated particles further downstream. Optionally, the gas stream is directed through a classifier and the coarse particles can be returned to the dispersion zone for further processing.

  However, in other exemplary embodiments, the filter cake is suspended with water to form a slurry. In other embodiments of the invention, a dispersant is added to the filter cake to form a slurry. Non-limiting examples of dispersants include polyacrylates, organic acids, naphthalene sulfonate / formaldehyde condensates, aliphatic alcohol polyglycol ethers, polypropylene ethylene oxide, polyglycol esters, polyamine ethylene oxide, sodium polyphosphate, sodium tripolyphosphate and polyvinyl alcohol Is included. The slurry is then dried by any of the known techniques for drying the slurry. This technique involves the spraying of inorganic fillers that are typically supplied by the use of nozzles and / or rotary atomizers. The atomized feed is then contacted with a hot gas, typically air, and the spray dried product is recovered from the hot gas stream. The contact with the atomized feed is carried out in the backflow or wake mode, and the gas temperature, atomization, contact and flow rate of the gas and / or atomized feed are controllable and have the desired properties. Can produce particles.

  Recovery of the dried product can be accomplished using a recovery technique such as filtration using a woven filter, or the dried particles are dropped for collection in a dryer where they can be removed, however, suitable Any of the collection techniques can be used. In a preferred embodiment, the product is recovered from the dryer using a particle filter, the product is placed at the bottom of the filter housing, the product is recovered therefrom using a screw conveyor, and then plumbed with compressed air. Can be carried through to silos.

The drying conditions can be appropriately selected by those skilled in the art who can apply conventional techniques and have ordinary skill. Generally these conditions include an inlet gas temperature typically between 250 ° C and 650 ° C and an outlet gas temperature typically between 105 ° C and 150 ° C.
Flame retardant application

The flame retardant of the present invention can be used as a flame retardant for various synthetic resins. Non-limiting examples of thermoplastic resins in which the flame retardant of the present invention can be used include olefins having 2 to 8 carbon atoms such as polyethylene, polypropylene, ethylene propylene copolymer, polybutene and poly (4-methylpentane-1). (Alpha olefin) polymers and copolymers, copolymers of these olefins and dienes, ethylene acrylate copolymers, polystyrene, ABS resins, AAS resins, AS resins, MBS resins, ethylene vinyl chloride copolymer resins, Ethylene vinyl acetate copolymer resin, ethylene vinyl chloride-vinyl acetate graft polymer resin, vinylidene chloride, polyvinyl chloride (chlorinated polyethylene) chlorinated polypropylene, vinyl chloride-propylene copolymer, vinyl acetate resin, phenoxy resin, Polyacetal, polyamide, polyimi , Polycarbonate, polysulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene terephthalate, polybutylene terephthalate, methacrylic resin. Further examples of suitable synthetic resins include natural or synthetic rubbers such as EPDM, butyl rubber, isoprene rubber, SBR, NIR, urethane rubber, polybutadiene rubber, acrylic rubber, silicone rubber, fluoroelastomer, NBR, and chlorosulfonated Polyethylene is also included. Further included are polymer suspensions (lattice).

  Preferably, the synthetic resin is a polyethylene resin (for example, high density polyethylene, low density polyethylene, linear low density polyethylene, ultra low density polyethylene, EVA (ethylene vinyl acetate resin), EEA (ethylene ethyl acrylate resin), EMA ( Ethylene acrylate copolymer resin), EAA (ethylene acrylate copolymer resin) and ultrahigh molecular weight polyethylene, polybutene, poly (4-methylpentane-1) and other olefins having 2 to 8 carbon atoms ( (Alpha olefins) polymers and copolymers, polyvinyl chloride and rubber.In a more preferred embodiment, the synthetic resin is a polyethylene-based resin.

  Thus, in one embodiment, the present invention relates to a flame retardant polymer formulation comprising at least one synthetic resin selected from the above, and in some embodiments, one of the flame retardants of the present invention or a flame retardant amount. , Any other flame retardant, to a finished object made from a flame retardant polymer formulation, for example by an extrusion or molding process.

  With the flame retardant amount of the flame retardant of the present invention, it generally means in the range of about 5% to 90% by weight, based on the weight of the flame retardant polymer formulation, more preferably about 10% with the same main component. % By weight to about 60% by weight. In the most preferred embodiment, the amount of flame retardant is from about 30% to about 60% by weight of the flame retardant of the present invention, with the same main component.

  In embodiments of the present invention, other flame retardants or combinations of different other flame retardants can be added to the polymer formulation. Non-limiting examples of these additional flame retardants are aluminum hydroxide, magnesium hydroxide, boehmite, layered double hydroxides (LDH), organically modified layered double hydroxides (LDHs), clay, organically modified Inorganic flame retardants such as nanoclay, zinc borate, zinc stannate, zinc hydroxyl stannate, brominated flame retardant, phosphorus-containing flame retardant, nitrogen-containing flame retardant and the like. (I) a synthetic hydrogarnet that is not modified or has been modified by inclusion of silicate and / or phosphate ions of its crystal structure and (ii) at least one inorganic system as described in this paragraph Combinations with flame retardants are typically used in relational quantities such that (i) :( ii) weight ratio is in the range of 99: 1 to 1:99, preferably 95: 5 to 5:95. The total amount of flame retardant combination used in or with the polymer is at least sufficient to retard combustion of the polymer used.

  The flame retardant polymer formulation can also include other additives commonly used in the prior art. Non-limiting examples of other additives suitable for the flame retardant polymer formulation of the present invention include polyethylene wax, silicon-based extrusion aids, extrusion aids such as fatty acids, amino-, vinyl-, alkylsilanes, maleic acid Binders such as fusion polymers, sodium or calcium stearate, organoperoxides, dyes, pigments, fillers, foaming agents, thermal stabilizers, antioxidants, antistatic agents, reinforcing agents, metal scavengers Alternatively, inactive agents, impact resistance improvers, processing aids, mold release aids, mold release agents, antiblocking agents, other flame retardants, UV stabilizers, plasticizers, flow aids, and the like are included. The ratio of other optional additives can vary appropriately for any demand of a given aspect, according to the prior art.

The method of incorporation and addition of the components of the flame retardant polymer formulation is not critical to the present invention and can be any of the known techniques as long as the method selected involves substantially homogeneous mixing.
For example, each of the above components and any optional additives used may also be a busconyder, a closed mixer, a Farrel continuous mixer, a twin screw extruder, or in some cases a single screw extruder or a two roll mill. Can be mixed. The flame retardant polymer formulation can be molded or extruded in the next processing step. In some embodiments, the apparatus can be used to thoroughly mix the components that form the flame retardant polymer formulation, and the object can be molded from the flame retardant polymer formulation.

  For extruded objects, any extrusion technique known to be effective for the synthetic resin mixture described above can be used. In one exemplary technique, the synthetic resin, the flame retardant of the present invention and optional ingredients, if selected, are compounded in a blender to form the flame retardant resin formulation described above. The flame retardant resin formulation is then heated to a molten state in an extruder and the molten flame retardant resin formulation is extruded through a selected mold to form an extruded object or used, for example, for data transmission Cover metal wire or glass fiber.

  In another embodiment of the present invention, the flame retardant polymer formulation of the present invention comprises at least one, and optionally more than one, synthetic resin selected from thermosetting resins. Non-limiting examples of thermosetting resins include epoxy resins, novolak resins, phosphorus-containing resins such as DOPO, such as brominated epoxy resins, unsaturated polyester resins and modified epoxy resins such as vinyl esters. The flame retardant resin formulation can also include other additives commonly used in the prior art. In addition to the above citations, non-limiting examples of other additives suitable for the flame retardant polymer formulation of the present invention include thermosetting agents such as solvents, curing agents or accelerators, dispersants or fine silica.

  In one embodiment of the invention, other flame retardants or combinations of different other flame retardants can be added to the thermosetting polymer formulation. Non-limiting examples of these additional flame retardants are aluminum hydroxide, magnesium hydroxide, boehmite, layered double hydroxides (LDH), organically modified layered double hydroxides (LDHs), clay, organically modified Inorganic flame retardants such as nanoclay, zinc borate, zinc stannate, zinc hydroxyl stannate, brominated flame retardant, phosphorus-containing flame retardant, nitrogen-containing flame retardant and the like. (I) a synthetic hydrogarnet that is not modified or has been modified by inclusion of silicate and / or phosphate ions of its crystal structure and (ii) at least one inorganic system as described in this paragraph Combinations with flame retardants are typically used in relational quantities such that (i) :( ii) weight ratio is in the range of 99: 1 to 1:99, preferably 95: 5 to 5:95. The total amount of this type of flame retardant combination used or shared in the thermosetting polymer formulation is at least sufficient to retard the combustion of the thermosetting polymer formulation used.

  The ratio of other optional additives can vary appropriately for any demand of a given aspect, according to the prior art. The preferred method of incorporation and addition of the components of the thermosetting polymer formulation is by high shear mixing. For example, by use of a high shear mixer manufactured by, for example, Silverson. Further processing of the resin-filler mixture is a common state of the art technique and is described in the literature. For example, for cured laminates, further processing of the resin-filler mixture to the “prepreg” stage and the cured laminate is described in “Epoxide Resin Handbook” published by McGraw-Hill Publishers, It is fully incorporated herein by reference.

In other embodiments of the present invention, the flame retardant polymer formulation of the present invention also includes at least one, and optionally two or more, polymer modified bitumen. Non-limiting examples of polymer modified bitumen include those modified with polypropylene and those modified with styrene butadiene styrene rubber. The flame retardant bitumen formulation can also include other additives commonly used in the prior art. Non-limiting examples of other additives suitable for the flame retardant polymer formulation of the present invention are the other additives described above. In still other embodiments of the present invention, other flame retardants or combinations of different other flame retardants can be added to the polymer modified bitumen formulation. The ratio of other optional additives can vary appropriately for any demand of a given aspect, according to the prior art.

  The foregoing description has set forth a number of embodiments of the invention. Those skilled in the art will recognize that other equally effective means can be devised to implement the spirit of the invention. It should also be emphasized that preferred embodiments of the present invention contemplate that all ranges discussed herein include from any low limit to any high limit. For example, the flame retardant amount of the flame retardant of the present invention can also include amounts in the range of about 70% to about 90% by weight, about 20% to about 70% by weight.

  Additional embodiments of the present invention include, but are not limited to:

  a) about 5% to about 90% by weight of at least one flame retardant comprising at least one synthetic resin or rubber and a synthetic hydrogarnet optionally modified by including silicon and / or phosphorus atoms in its crystal structure A flame retardant polymer formulation comprising a cubic form where the synthetic hydrogarnet is not modified by containing silicon atoms and / or phosphorus atoms, and optionally, at least one other A flame retardant polymer formulation having a flame retardant additive.

  b) The flame retardant polymer formulation according to a), wherein the synthetic resin is selected from thermoplastic resins, thermosetting resins and polymerizable suspensions.

  c) The flame retardant polymer formulation according to a), wherein the synthetic resin is a polyolefin resin.

  d) The flame retardant polymer formulation according to a), wherein the synthetic resin is an epoxy resin.

  e) The flame retardant polymer formulation according to a), wherein the synthetic resin is a polyester resin.

  f) from about 5% to about 90% by weight of at least one polymer-modified bitumen and at least one flame retardant comprising a synthetic hydrogarnet optionally modified by including silicon and / or phosphorus atoms in its crystal structure. % Of the flame retardant polymer formulation, wherein the synthetic hydrogarnet has a cubic shape when it is not modified by containing silicon atoms and / or phosphorus atoms, optionally at least one other A flame retardant polymer formulation having a flame retardant additive.

  g) The flame retardant additive is aluminum hydroxide, magnesium hydroxide, boehmite, layered double hydroxide, organically modified layered double hydroxide, clay, organically modified nanoclay, zinc borate, zinc stannate. And a flame retardant polymer formulation according to a) or f) selected from zinc stannate, brominated flame retardant, phosphorus-containing flame retardant, and nitrogen-containing flame retardant.

  h) The flame retardant polymer formulation is an extrusion aid, binder, solubilizer, curing agent, dye, pigment, filler, foaming agent, thermal stabilizer, antioxidant, antistatic agent, reinforcing agent, At least one additional additive selected from metal scavengers or deactivators, impact modifiers, processing aids, mold release aids, lubricants, antiblocking agents, UV stabilizers, plasticizers and flow aids A flame retardant polymer formulation according to a) or g).

i) The flame retardant polymer formulation according to any one of a) to h), wherein the flame retardant has the following empirical formula:
(A) M ^II ₃ M ^III ₂ (OH) _12-4x (SiO ₄ ) _x , wherein M ^II is a Group IIA metal atom, M ^III is a Group IIIA metal atom, and x is about 0.05 to A number in the range of about 1.5, or
_{^{(B) M II 3 M III}} 2 O y (OH) 12-5y (PO 4) y, M II and ^{M III} in the formula are as defined in (A), y is from about 0.05 to about 1 A number in the range of .5, or
(C) M ^II ₃ M ^III ₂ O _y (OH) _12-5y-4x (PO ₄ ) _y (SiO ₄ ) _x , wherein M ^II and M ^III are as defined in (A), where x is As defined in (A) and y is as defined in (B), provided that the sum of x + y is a number ranging from about 0.05 to about 1.5, or
(D) M ^II ₃ M ^III ₂ (OH) ₁₂ , wherein M ^II and M ^III are the same as defined in (A).

  j) The flame retardant polymer formulation according to i), wherein the synthetic composition has the empirical formula of (A).

  k) The flame retardant polymer formulation according to i), wherein the synthetic composition has the empirical formula of (B).

  l) The flame retardant polymer formulation according to i), wherein the synthetic composition has the empirical formula of (B).

  m) The flame retardant polymer formulation according to i), wherein the synthetic composition has the empirical formula of (D).

n) M ^II is (i) Ca, Sr or Ba, (ii) a mixture of at least two of Ca, Sr or Ba, (iii) a mixture of Mg and one or more of Ca, Sr or Ba Wherein less than about 50% by weight of the mixture of (iii) is Mg and M ^III is (i) Al or (ii) a mixture of Al and one or more of B, Ga, In, Tl The flame retardant polymer formulation according to any of i) to m), wherein less than about 20% by weight of the mixture of (ii) is one or more of B, Ga, In, Tl.

o) The flame retardant polymer formulation according to n), wherein at least about 98% by weight of M ^II is Ca and at least about 98% by weight of M ^III is Al.

The following examples are given for illustration. They are not intended to be limiting and should not be construed as limiting the invention to the details described herein.
General procedure

The general procedure used in these examples for synthesizing the novel inorganic modified hydrogarnet flame retardant provided by the present invention was as follows: 20 with external heating source and propeller stirrer Fill the liter container with the specified amount of water and alkali hydroxide. While stirring, the mixture is heated until the appropriate temperature is reached, and aluminum trihydroxide (ATH), a suitable calcium compound and a suitable silicon compound are then added in the proper form and in the appropriate amount and the addition time is increased. write down. The preparation mixture is continuously stirred at the specified temperature for 4 hours. At this point, the mixture is removed from the container and cooled to room temperature. The slurry-like preparation mixture is then filtered through a filter press and washed with distilled water until the conductivity of the wash water reaches less than 500 microseconds. Recombine the filter cake and re-slurry with water. The prepared slurry is then dried in a Buchi laboratory spray dryer, type B-290, operating at an inlet temperature of 220 ° C and an outlet temperature of about 80 ° C. The rate of moisture evaporation is approximately 1 liter per hour.
Test method

The methods used to determine the results and properties of the compositions produced and evaluated in the examples are as follows:
A) BET surface area was measured by DIN-66132.
B) The median number (d ₅₀ ) of the particle size distribution was measured by laser diffraction using a Beckman Coulter LS 13 320 according to ISO 13320. The following detailed procedure is used: a suitable aqueous-dispersant aqueous solution is subjected to background measurement of the aqueous solution on a Beckmann particle size analyzer. Approximately 0.5 g of the sample to be measured is dispersed in the same water-dispersant aqueous solution used in the subsequent background measurement, thus forming a suspension. This suspension is sonicated at 200 W for 2 minutes, then introduced into the apparatus by pipette and continued until the optimum measured concentration specified by the manufacturer is reached. In the application software, select the appropriate parameters for the sample, ie the measurement conditions including the refractive index and the PIDS detector for the nano range. Thereafter, the particle size distribution data is collected at 90 second intervals and analyzed by Mie scattering theory. To formulate the water / dispersant aqueous solution used in these determinations, it is possible to formulate the concentrate first from 500 grams of registered Calgon dispersant, from KMF Laborchemie, and from 3 liters of CAL Polysalt, BASF. Convenient. This aqueous solution is formulated up to 10 liters using deionized water. Then, 100 ml out of 10 liters of this stock solution is taken out, this time diluted to 10 liters with deionized water, and the final aqueous solution is used as the water-dispersant aqueous solution described above.
C) Thermogravimetric analysis (TGA) was performed using a Mettler Toledo TGA / SDTA 851e Mettler Toledo TGA / SDTA 851e instrument. In this analysis, a 70 μl alumina crucible (approximately 180 mg initial weight) with a lid under nitrogen (25 ml per minute) was used. The heating rate used was 1 ° C. per minute. D) Flame photometric determination of sodium oxide content was performed using Dr. Lang's flame photometer M7DC or M8D Propan.
E) X-ray powder diffraction (XRD) is performed on a Siemens D500 instrument with Bragg-Brentano focusing, applying a copper anode with a nickel filter for monochromation.
F) Conical calorimetry measurement was performed on a compression molded plate having a thickness of 3 mm in accordance with ASTM E 1354 under the condition of 35 kW / m ² . The peak exotherm rate (PHRR) shown in Table 2 is the maximum amount of heat released during the burning of the cone calorimeter sample. If there is a second peak during the burning of the cone calorimeter sample, the value of the heating rate (HRR) is also measured. The time to ignition (TTI) value shown in Table 2 is the time that the sample ignites upon thermal exposure to the cone calorimeter. MARHE (Maximum of the Average Rate of Heat Emission) is the maximum value of the average rate of heat generation.

Examples 1-8, 10 and 11 are intended to illustrate the novel flame retardants of the present invention and methods for their preparation. Examples 9 and 12 are presented for comparison purposes.
Example 1 (Invention)

In this example, the initial charge for a 20 liter container was 4 liters of water followed by 324 g of NaOH. The mixture was heated to 95 ° C. at a rate of about 15 ° C. per minute with stirring. When the desired temperature is reached, 413 g of finely precipitated aluminum trihydrate is added, followed by 587 g of calcium hydroxide, and water glass (Na ₂ Si ₃ O ₇ with a calculated SiO ₂ concentration of 27% by weight. ) 93 g of sodium silicate aqueous solution (Riedel-de Haen) was added. This provides a theoretical amount equivalent to 0.15 molar equivalents of silicate per mole of synthetic flame retardant, resulting in the product Ca ₃ Al ₂ (OH) _11.4 (SiO ₄ ) _0.15 . The mixture was stirred for 2 hours and maintained at that temperature. The results of the analysis and determination of the synthetic inorganic modified flame retardant obtained as a result are summarized in Table 1. An SEM photograph of the octahedral crystal shape of this product is shown in FIG. Note that the “SiO ₂ ” concentration is a calculated value for calculation purposes only. It does not mean that SiO ₂ actually exists.
Example 2 (Invention)

In this example, the initial fill for a 20 liter container was 4 liters of water followed by 444 g of NaOH. The mixture was heated to 95 ° C. at a rate of about 15 ° C. per minute with stirring. When the desired temperature is reached, 413 g of finely precipitated aluminum trihydrate is added, followed by 587 g of calcium hydroxide, and water glass (Na ₂ Si ₃ O ₇ with a calculated SiO ₂ concentration of 27% by weight. 587 g of sodium silicate aqueous solution (made by Riedel-de Haen) was added. This provides a theoretical amount equivalent to 0.3 molar equivalents of silicate per mole of synthetic flame retardant, resulting in the product Ca ₃ Al ₂ (OH) _10.8 (SiO ₄ ) _0.3 . The mixture was stirred for 2 hours and maintained at that temperature. The results of the analysis and determination of the synthetic inorganic modified flame retardant obtained as a result are summarized in Table 1.
Example 3 (Invention)

In this example, the initial fill for a 20 liter container was 14,2 liters of water, followed by 3.55 kg of Solvay alcoholic beverage and 50 wt% concentrated NaOH. The mixture was heated to 95 ° C. at a rate of about 1 ° C. per minute with stirring. When the desired temperature is reached, 1850 g of finely precipitated aluminum trihydrate is added, followed by 2340 g of calcium hydroxide, and water glass (Na ₂ Si ₃ O ₇ with a calculated SiO ₂ concentration of 27% by weight. ) Of sodium silicate aqueous solution (made by Riedel-de Haen) was added.
This provides a theoretical amount equivalent to 0.3 molar equivalents of silicate per mole of synthetic flame retardant, resulting in the product Ca ₃ Al ₂ (OH) _10.8 (SiO ₄ ) _0.3 . The mixture was stirred for 1 hour and maintained at the temperature. The results of the analysis and determination of the synthetic inorganic modified flame retardant obtained as a result are summarized in Table 1.
Example 4 (Invention)

In this example, the initial charge for a 20 liter container was 4 liters of water, followed by 705 g of NaOH. The mixture was heated to 95 ° C. at a rate of about 15 ° C. per minute with stirring. When the desired temperature was reached, 413 g of finely precipitated aluminum trihydrate was added, followed by 587 g of calcium hydroxide, and an additional 92 g of phosphoric acid having a concentration of 85 wt% H ₃ PO ₄ . This provides a theoretical amount equivalent to 0.3 molar equivalents of silicate per mole of synthetic flame retardant, resulting in the product Ca ₃ Al ₂ O _0.3 (OH) _10.5 (PO ₄ ) _0.3. It is done. The mixture was stirred for 2 hours and maintained at that temperature. The results of the analysis and determination of the synthetic inorganic modified flame retardant obtained as a result are summarized in Table 1.
Example 5 (Invention)

A 20 liter container is filled with 4 liters of water, 444 g of sodium hydroxide, then 413 g of fine precipitated aluminum trihydrate is added, and 587 g of calcium hydroxide is added, and a synthetic hydrogarnet Ca ₃ Al ₂ ( OH) ₁₂ was obtained. The mixture was then heated at 85 ° C. for 2 hours. The pH of the slurry after 4 hours was 12.1. The results of analysis and determination of the unmodified synthetic calcium aluminate flame retardant obtained as a result are summarized in Table 1. A cubic SEM photograph of this product is shown in FIG.

Table 1 shows that the flame retardant material of the invention has a much higher thermal stability, indicated by the LEO of aluminum trihydroxide (ATH), a commercial ATH flame retardant Martinol OL-104 produced by Martinswerk. . It further shows that the thermal stability of the silicate and phosphate modified hydrogarnet materials (Examples 1-4) is higher compared to the unmodified hydrogarnet (Example 5).
Example 6 (Invention)

ExxonMobil's registered trademark Escorene Ultra UL00119 ethylene vinyl acetate copolymer (EVA) 100 phr (about 396.9 g) and 150 phr (about 595.3 g) of the flame retardant of the present invention produced in Example 1 are produced by Evonik Aminosilane AMEO1 0.2 phr (about 4.8 g) and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (registered trademark Ethanox 310 antioxidant manufactured by Albemarle) 0.75 phr (about 3.0 g) and mixed on a Collin two roll mill W150M for about 20 minutes. Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 130 ° C. The prepared compound was removed from the pulverizer, cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. FIG. 1 is a conical calorimeter heat release rate curve measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 2 shows the characteristic values of the conic curve (that is, PHRR, TTI, MARHE, heat release rate (HRR), and second maximum value time).
Example 7 (Invention)

ExxonMobil's registered trademark Escorene Ultra UL00119 ethylene vinyl acetate copolymer (EVA) 100 phr (about 396.9 g) and the inventive flame retardant 150 phr (about 595.3 g) produced in Example 2 are produced by Evonik's aminosilane AMEO 1 0.2 phr (about 4.8 g) and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (registered trademark Ethanox 310 antioxidant manufactured by Albemarle) 0.75 phr (about 3.0 g) and mixed on a Collin two roll mill W150M for about 20 minutes. Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 130 ° C. The prepared compound was removed from the pulverizer, cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. FIG. 2 is a conical calorimeter heat release rate curve measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 2 shows the characteristic values of the conic curve (that is, PHRR, TTI, MARHE, heat release rate (HRR), and second maximum value time).
Example 8 (Invention)

ExxonMobil's registered trademark Escorene Ultra UL00119 ethylene vinyl acetate copolymer (EVA) 100 phr (about 396.9 g) and the comparative additive 150 phr (about 595.3 g) produced in Example 5 are aminosilane AMEO 1.2 phr made by Evonik. (About 4.8 g) and Albemarle registered trademark Ethanox 310 antioxidant 0.75 phr (about 3.0 g) on a Collin two roll grinder W150M for about 20 minutes. Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 130 ° C. The prepared compound was removed from the pulverizer, cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. FIG. 3 is a conical calorimeter heat release rate curve measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 2 shows the characteristic values of the conic curve (that is, PHRR, TTI, MARHE, heat release rate (HRR), and second maximum value time).
Example 9 (comparison)

ExxonMobil's registered trademark Escorene Ultra UL00119 ethylene vinyl acetate copolymer (EVA) 100 phr (about 396.9 g) and a commercial ATH flame retardant Martin OL-104 LEO 150 phr (about 595.3 g) produced by Martinswark. With Evonik aminosilane AMEO 1.2 phr (about 4.8 g) and Albemarle registered trademark Ethanox 310 antioxidant 0.75 phr (about 3.0 g) on a Collin two roll mill W150M. Mixed for minutes. Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 130 ° C. The prepared compound was removed from the pulverizer, cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. 1, 2 and 3 are conical calorimeter heat release rate curves measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 2 shows the characteristic values of the conic curve (that is, PHRR, TTI, MARHE, heat release rate (HRR), and second maximum value time). In Table 2, Examples 6, 7 and 8 are examples of the present invention, while Example 9 is a comparative example.

Table 2 shows that the PHRR of Inventive Example 7 is significantly lower than Comparative Example 9. The PHRR of Invention Examples 6 and 8 is equal to the PHRR of Example 9 within experimental error, but FIGS. 1, 2 and 3 show that after the initial peak, the heat release rate of the invention example is comparative Example 9. Lower, thereby exhibiting good flame retardant properties. In Invention Examples 6 and 7 and Invention Example 8, MARHE is also decreased.

The time value corresponding to the second maximum value of the conic curve is generally correlated with the char formation potential of the filler, and the stronger the char, the longer the appearance time of the second peak peak. Table 2 shows that "Invention Examples 6, 7 and Example 8" all have significantly longer "time to second peak" than Comparative Example 9, suggesting the highest level of technology for inorganic flame retardant fillers. . In addition, the heat release rate of the second peak is considerably lower in the inventive examples 6, 7 and 8 than in the comparative example 9, and it is necessary to pay attention together with the absolute value related to PHRR in each example.
Example 10 (Invention)

ExxonMobil registered trademark Escorene Ultra UL00328 ethylene vinyl acetate copolymer (EVA) 67 phr (about 333,8 g) and ExxonMobil linear low density polyethylene (LLDPE) LL1001XV 17 phr (about 84.7 g) Random terpolymer Lotader 3210 8 phr (about 39.9 g) of Ethylene (E), butyl acrylate (BA) and maleic anhydride (MAH) manufactured by Arkema, Inc. MAH fusion LLDPE Fusbond MB 226D 8 phr (about 39.9 g) and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyethyl) Pionato) (and mixed for about 20 minutes at Albemarle Corporation trademark Ethanox310 antioxidant) 0.75 phr (Collin Co. two-roll mill on W150M with about 3.7 g). Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 150 ° C. The prepared compound was removed from the pulverizer and cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. FIG. 4 is a conical calorimeter heat release rate curve measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 3 shows the characteristic values (that is, PHRR, TTI, MARHE, heat release rate (HRR) and second maximum time) of the conic curve.
Example 11 (Invention)

ExxonMobil registered trademark Escorene Ultra UL00328 ethylene vinyl acetate copolymer (EVA) 67 phr (about 333,8 g) and ExxonMobil linear low density polyethylene (LLDPE) LL1001XV 17 phr (about 84.7 g) Random terpolymer Lotader 3210 8 phr (about 39.9 g) of Ethylene (E), butyl acrylate (BA) and maleic anhydride (MAH) manufactured by Arkema, Inc. MAH fusion LLDPE Fusbond MB 226D 8 phr (about 39.9 g) and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyethyl) Pionato) (and mixed for about 20 minutes at Albemarle Corporation trademark Ethanox310 antioxidant) 0.75 phr (Collin Co. two-roll mill on W150M with about 3.7 g). Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 150 ° C. The prepared compound was removed from the pulverizer and cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. FIG. 5 is a conical calorimeter heat release rate curve measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 3 shows the characteristic values (that is, PHRR, TTI, MARHE, heat release rate (HRR) and second maximum time) of the conic curve.
Example 12 (comparison)

ExxonMobil® registered trademark Escorene Ultra UL00328 ethylene vinyl acetate copolymer (EVA) 67 phr (about 333,8 g) and ExxonMobil linear low density polyethylene (LLDPE) LL1001XV 17 phr (about 84.7 g) and produced by Martinswark Commercially available ATH flame retardant Martinol OL-104 LEO 100 phr (about 498.1 g) and random terpolymer Lotader 3210 8 phr of ethylene (E), butyl acrylate (BA) and maleic anhydride (MAH) manufactured by Arkema 9 g), DuPont MAH fusion LLDPE Fusbond MB 226D 8 phr (about 39.9 g) and pentaerythritol tetrakis (3- 3,5-di-tert-butyl-4-hydroxyethyl) propionate) (registered trademark Ethanox 310 antioxidant from Albemarle) on a two-roll mill W150M from Collin with 0.75 phr (about 3.7 g) Mix for about 20 minutes. Mixing on the two-roll mill was done in a conventional manner well known to those skilled in the art. The temperature of the two rollers was set to 150 ° C. The prepared compound was removed from the pulverizer and cooled to room temperature, and then the particle size was further reduced to obtain a granular material suitable for compression molding with a two platen press. 4 and 5 are conical calorimeter heat release rate curves measured at 35 kW / m ² on a compression molded plate having a thickness of 3 mm. Table 3 shows the characteristic values (that is, PHRR, TTI, MARHE, heat release rate (HRR) and second maximum time) of the conic curve.

  It should be noted that the polymer formulations of Examples 10-12 are different, the amount of filler is quite low, and the two formulations should not be compared with each other.

  It can be seen from Table 3 that the PHRR of Inventive Examples 10 and 11 is significantly lower than Comparative Example 12. 4 and 5 show that the heat release rate of the inventive example after the initial peak is considerably lower than that of Comparative Example 11, indicating better flame retardant properties. In the inventive example, MARHE is also decreased.

  The time value corresponding to the second maximum value of the conic curve is generally correlated with the char formation potential of the filler, and the stronger the char, the longer the appearance time of the second peak. Table 3 shows the “time to second peak” for Inventive Examples 10 and 11 which is considerably longer than Comparative Example 12. Example 12 suggests the highest level of technology for inorganic flame retardant fillers. It should be noted that the heat release rate of the second peak is considerably lower in the inventive examples 10 and 11 than in the comparative example 12.

Components referred to by chemical name or formula anywhere in this specification or claim may be singular or plural in their chemical name or chemical type (eg, other components, solubilizers). Etc.) are identified prior to contact with other substances referred to. Whatever chemical changes, chemical transformations and / or chemical reactions occur, certain components are required in accordance with this disclosure to be generated in such mixtures or solutions resulting from such changes, transformations and / or reactions. It is not important that it is a natural result summarized under certain conditions. In this way, the ingredients are identified as raw materials that are brought together in connection with performing the desired operation or in forming the desired composition. In addition, even if the following claims refer to a substance, component and / or raw material in the present tense (“includes”, “is”, etc.), that reference is made to the substance, component or raw material according to the present disclosure. Applied to what was present just before the first contact, compounding or mixing with one or more other substances, components and / or ingredients. The fact that a substance, component or raw material could have lost its initial identity by chemical reaction or transformation during the contacting, blending or mixing operation process, as implemented by the ordinary skill of a chemist, according to this disclosure, Not a real concern. Each or any patent or publication mentioned in any part of this specification is relevant to this disclosure as a reference and is treated as if it were described herein.

  Unless expressly indicated otherwise, the article “a” or “an” as used herein is not intended to limit the claim to the single element that the article refers to. Rather, unless the context clearly indicates otherwise, the article “a” or “an” as used herein is intended to encompass one or more of the above elements.

  The present invention includes, consists of, or may consist essentially of the materials and / or procedures detailed herein.

  The present invention is susceptible to significant variations in its practical use. Accordingly, the foregoing description is not intended to be construed as limiting, but is intended to limit the invention to the specific examples and the like presented hereinabove.

Claims (22)

  A flame retardant comprising a synthetic hydrogarnet that is optionally modified by including silicon atoms and / or phosphorus atoms in the crystal structure, when there is no modification by containing silicon atoms and / or phosphorus atoms, A flame retardant in which the synthetic hydrogarnet has a cubic shape. The flame retardant according to claim 1, which has any one of the following empirical formulas:
(A)
Where M ^II is a Group IIA metal atom, M ^III is a Group IIIA metal atom, and x is a number in the range of about 0.05 to about 1.5, or
(B)
Where M ^II and M ^III are as defined in (A) and y is a number in the range of about 0.05 to about 1.5, or
(C)
Wherein M ^II and M ^III are the same as defined in (A), x is the same as defined in (A), and y is the same as defined in (B), provided that the sum of x + y is about 0. A number ranging from 05 to about 1.5, or
(D)
In the formula, M ^II and M ^III are the same as defined in (A).   The flame retardant according to claim 2, wherein the synthetic hydrogarnet has an empirical formula of (A).   The flame retardant according to claim 2, wherein the synthetic hydrogarnet has the empirical formula (B).   The flame retardant according to claim 2, wherein the synthetic hydrogarnet has an empirical formula of (C).   The flame retardant according to claim 2, wherein the synthetic hydrogarnet has an empirical formula of (D). M ^II is (i) a mixture of at least two of Ca, Sr or Ba, (ii) Ca, Sr or Ba, or (iii) a mixture of Mg and one or more of Ca, Sr or Ba Less than about 50% by weight of the mixture of (iii) is Mg and M ^III is a mixture of (i) Al or (ii) Al and one or more of B, Ga, In, Tl The flame retardant according to any one of claims 2 to 6, wherein less than about 20% by weight of the mixture of (ii) is one or more of B, Ga, In, Tl. 8. The flame retardant of claim 7, wherein at least about 98% by weight of M ^II is Ca and at least about 98% by weight of M ^III is Al. Process for forming a compound having the following empirical formula:
a)
Where M ^II is a Group IIA metal atom, M ^III is a Group IIIA metal atom, and x is a number in the range of about 0.05 to about 1.5.
b)
Wherein M ^II and M ^III are as defined in a) and y is a number ranging from about 0.05 to about 1.5.
c)
Wherein M ^II and M ^III are the same as defined in a), x is the same as defined in a), y is the same as defined in b), provided that the sum of x + y is 0.05 to about 1 A number in the range of .5.
d)
In which M ^II and M ^III are as defined in a) and this process comprises:
i) (1) Group IIIA metal source (2) Group IIA metal source (3) Silicon source when forming a compound of formula a) or c), (4) When forming a compound of formula b) or c) Stirring a mixture formed of a phosphorus source of (5) and an alkali metal hydroxide;
ii) heating the mixture at a temperature in the range of about 50 ° C to about 100 ° C; and
iii) optionally cooling the reaction product, or cooling the reaction product, wherein the ratio of the Group IIIA metal source to the Group IIA metal source used in forming the mixture is Group IIA metal: Group IIIA metal And wherein the silicon source forming the mixture is about 0.05 moles to 1 mole of the compound to be formed. The phosphorus source used to provide an amount of silicate in the range of about 1.5 moles and / or to form the mixture is from about 0.05 moles per mole of compound to be formed. Used to provide an amount of phosphate in the range of about 1.5 moles.   The process according to claim 9, wherein said compound has the empirical formula of a).   The process according to claim 9, wherein said compound has the empirical formula of b).   The process of claim 9 wherein the compound has the empirical formula of c).   The process of claim 9 wherein the compound has the empirical formula of d).   Said mixture (1) is an aluminum source and / or said mixture (2) is a calcium source and / or said mixture (3) is an aqueous silicate solution or crystalline silicon dioxide, 10. Process according to claim 9, wherein the mixture (4) is an aqueous phosphate solution. In the above mixture, the aluminum source is aluminum hydroxide, boehmite, pseudoboehmite, aluminum oxide or a mixture of two or more of the foregoing, and / or the calcium source is an inorganic salt, hydroxide or a hydrate thereof. And / or the aqueous silicate solution is one or more solutions of NaSiO ₃ or Na ₂ Si ₃ O ₇ and / or the aqueous phosphate solution is phosphoric acid 15. The process of claim 14, which is a solution of one or more of alkali, ammonium phosphate, alkali or ammonium diphosphate and / or alkali or ammonium polyphosphate.   At least one synthetic resin, rubber or at least one polymer-modified bitumen and from about 5% to about 90% by weight of at least one flame retardant according to any one of claims 1 to 7, optionally And a flame retardant polymer formulation comprising at least one other flame retardant additive.   The flame retardant polymer formulation of claim 16, wherein the formulation comprises a synthetic resin, and the synthetic resin is selected from a thermoplastic resin, a thermosetting resin, and a polymer suspension. .   The flame retardant polymer formulation according to claim 16, wherein the formulation includes a synthetic resin, and the synthetic resin is a polyolefin resin.   The flame retardant polymer formulation according to claim 16, wherein the formulation includes a synthetic resin, and the synthetic resin is an epoxy resin.   The flame retardant polymer formulation according to claim 16, wherein the formulation includes a synthetic resin, and the synthetic resin is a polyester resin.   The flame retardant additive includes aluminum hydroxide, magnesium hydroxide, boehmite, layered double hydroxide, organically modified layered double hydroxide, clay, organically modified nanoclay, zinc borate, stannic acid The flame retardant polymer formulation according to claim 16 selected from zinc and zinc hydroxystannate, brominated flame retardant, phosphorus containing flame retardant, nitrogen containing flame retardant.   The flame retardant polymer formulation contains an extrusion aid, a binder, a solubilizer, a curing agent, a dye, a pigment, a filler, a foaming agent, a heat stabilizer, an antioxidant, an antistatic agent, a reinforcing agent, a metal trap. At least one additional additive selected from collectors or deactivators, impact modifiers, processing aids, mold release aids, lubricants, antiblocking agents, UV stabilizers, plasticizers and flow aids A flame retardant polymer formulation according to claim 16 comprising: